JPH07114800B2 - Layered coating material - Google Patents

Abstract

A stiff, water resistant laminated medical or veterinary dressing is described along with a procedure for forming the final hardened dressing. The dressing is obtained by treating a gypsum bandage with an aqueous dispersion of a synthetic resin and then forming a layer from it which is immediately adjacent to a layer formed from a water hardenable synthetic resin bandage. Either layer may be formed first and further layers may be formed so long as the layers alternate between those formed from wraps of the gypsum bandages and those formed from wraps of the synthetic resin bandage.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to Iaminated dressings for use in medical or veterinary applications.

It is known to use bandages impregnated with gypsum as a cured coating material. The coating material of such a cast is undesirably heavy, has a low permeability to air, and in the wet state, for example, when water acts on the cured coating material, it rapidly loses its strength and absorbs or scatters X-rays. To prevent radiographic diagnosis, and often to irritate the skin due to bacteria or mold growth to retain water.

Supporting coating materials are also known, which consist of woven carrier materials or glass fiber-based carrier materials made of polymers, for example synthetic materials coated with polyurethane which cure in the presence of water [Chemical Orthopedic and・
Related Research (Chemical Orthopaedices and
Related Research), 103 , 109-117 (1974), and German Patent Publication No. 2,357,931 and U.S. Pat. Nos. 4,376,438, 4411262, and 4570622].
Supporting coating materials based on synthetic materials are not very formable.

According to the invention, a cast and a water-curable synthetic resin are each provided as a separate layer on the carrier material, at least the cast layer being based on a synthetic dispersion of polyurethane, a synthetic dispersion of polyurethaneurea or polyvinyl acetate. Laminated coating materials have been found that have been finished with the synthetic dispersions described above.

The laminated coating material of the present invention has a high degree of moldability,
At the same time, it has a high degree of stability against destruction.

The cast for the laminated coating material of the present invention can be dehydrated (eg anhydrous) or fully or partially hydrated calcium sulphate, and also an additive for processing a cast dressing on a support material. Can be included.

This additive should improve, for example, the adhesion of the textile to the carrier and increase the resistance of the cured cast to water. Additives are generally added with calcium sulfate during the manufacture of casts.

Additives are, for example, inorganic salts, such as diatomaceous earth, chalk, aluminosilicates and kaolin, or organic plastics, such as alkylaryl sulfonates, lignin-sulfonates, melamine resins or cellulose ethers,
And can be starch ether [Ulman
lman) 1976, Vol. 12, p. 306].

The plaster bandages described above are known per se.

The water-curable synthetic resin is preferably a polyurethane-based resin or a polyvinyl resin.

All the water-curable polyurethanes which can be used according to the invention are organic polyisocyanates known per se. That is, it can be any desired compound containing at least two organically bonded isocyanate groups in one molecule or a mixture thereof. Some of these have a molecular weight
A low molecular weight polyisocyanate of 400 or less, and thus a low molecular weight polyisocyanate having, for example, a molecular weight of 400 to 1
It includes both modified products modified with 0,000, preferably 600-8,000, especially 800-5,000. The molecular weight can be calculated from functional group analysis and functional group content.
Suitable low molecular weight polyisocyanates include, for example, the formula Q (NOC) _n, where n is 2-4, preferably 2-3, and Q is an aliphatic carbon number of 2-18, preferably 6-10. Hydrogen group, alicyclic hydrocarbon group having 4 to 15 carbon atoms, preferably 5 to 10 carbon atoms, aromatic hydrogen carbon group having 6 to 15 carbon atoms, preferably 6 to 13 carbon atoms, 8 to 15 carbon atoms, preferably 8 to Included are those that have 13 aliphatic-aromatic hydrocarbon groups.

Low molecular weight polyisocyanates of this kind are, for example, hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane 1,3-diisocyanate, cyclohexane 1,3- and 1,4-diisocyanates and any desired mixtures thereof, 1-isocyanate. -3,3,5-Trimethyl-5-isocyanatomethylcyclohexane, 2,4
-And 2,6-hexahydrotoluylene diisocyanate and any desired mixture of these isomers, hexahydro-
1,3- and / or -1,4-phenylene diisocyanate,
Burhydro-2,4'- and / or 4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluylene diisocyanate and any desired isomers thereof A mixture of diphenylmethane 2,4'- and / or 4,4'-diisocyanate, naphthylene 1,5-diisocyanate, triphenylmethane
4,4 ', 4 "-triisocyanate or polyphenylene-polymethylene polyisocyanate, eg aniline /
It is obtained by subjecting the formaldehyde condensate to phosgenation.

Suitable high molecular weight polyisocyanates are modified products of simple polyisocyanates, i.e., for example, isocyanurates, carboimides, allophanates, burettes or uretdione structures, such as may be prepared by conventional methods from simple polysocyanates of the above general formula. It is a polyisocyanate having units. Among the high molecular weight modified polyisocyanates, the prepolymers known in urethane chemistry having terminal isocyanate groups in the molecular weight range of 400 to 10,000, preferably 600 to 8,000, especially 800 to 5,000, are particularly suitable. These compounds are prepared in a known manner by reacting an excess of a simple polyisocyanate of the abovementioned type with an organic compound having at least two groups which are reactive towards isocyanate groups, in particular polyhydroxy compounds. Suitable polyhydroxy compounds of this type are simple polyhydroalcohols such as ethylene glycol, trimethylolpropane, propane-1,2-diol or butane-1,2-diol, especially those having molecular weight ranges from 600 to 600 known in polyurethane chemistry. 8,000, preferably 800-
High molecular weight polyether-polyols and / or polyester-polyols having at least 2 and generally 2-8, preferably 2-4, primary and / or secondary hydroxyl groups at 4,000. Of course, for example, NCO-prepolymers obtained from the abovementioned low molecular weight polyisocyanates and less suitable compounds having groups which are reactive towards isocyanate groups, such as polythioethers
Polyols, polyacetals containing hydroxyl groups, polyhydroxy-polycarbonates, polyester-amides containing hydroxyl groups, or copolymers of olefinic unsaturated compounds containing hydroxyl groups can be used. Compounds suitable for the preparation of NCO-prepolymers and having groups which are reactive towards isocyanate groups, in particular hydroxyl groups, are described, for example, in US Pat. No. 4,218,543, column 7, line 29 to column 9, line 25. . During the preparation of the NCO-prepolymer, these compounds having groups which are reactive towards isocyanate groups are reacted with, for example, the abovementioned simple polyisocyanates and the NCO / OH equivalent weight is kept above 1. Generally, the NCO content of the NCO-prepolymer is 2.5-30, preferably 6-25% by weight. In this regard, the terms "NCO-prepolymer" or "prepolymer having an isocyanate group at the end" are used herein to mean the reaction product itself, as well as a mixture of it with an excess of unreacted polyisocyanate. And often referred to as "semi-prepolymer".

Particularly suitable polyisocyanate components for the present invention are the industrial polyisocyanates commonly used in polyurethane chemistry, namely hexamethylene diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone. Diisocyanate, abbreviated IPDI), 4,4'-diisocyanatodicyclohexylmethane, 4,4'-diisocyanatodiphenylmethane, its corresponding mixture with 2,4'- and 2,2'-isomers, of the diphenylmethane series Polyisocyanate mixtures, such as those obtained by phosgenation of aniline / formaldehyde condensates by known methods, modified products of these industrial polyisocyanates containing burette or isocyanurate groups, especially on the one hand these industrial polyisocyanates The base The NCO- prepolymer was, while simple polyols with, and / or polyether - polyols, and such polyisocyanates any desired mixtures - polyols, and / or polyester. Isocyanates with aromatically bound NCO groups are preferred for the present invention. A particularly suitable polyisocyanate component in the present invention is the partially carbodiimidated diisocyanate diphenylmethane, which may also contain uretonimine groups resulting from the addition of monomeric diisocyanates to the carbodiimide structure.

A water-curable polyvinyl resin is, for example, a vinyl compound composed of a hydrophilic prepolymer having two or more polymerizable vinyl groups, in which a solid, insoluble vinyl redox contact is embedded, and one of its constitutions is The components are surrounded by a water soluble or water permeable envelope. Such a redox catalyst is, for example, sodium bisulfite / copper (II) sulphate, where for example copper sulphate is surrounded by 2-hydroxyethyl polymethacrylate.

Supporting synthetic coating materials based on water-curable polyvinyl resins are described, for example, in EP 0,136,021.

The cast and synthetic resin layer carrier materials for the laminated coating materials of the present invention can be the carrier materials conventionally used for supporting coating materials.

Possible carrier materials are solid or porous films or foams of natural or synthetic materials (eg polyurethane), especially on textile substrates which are permeable to air, preferably with a weight per unit area of 20. ~ 1,000 g / m ² , especially 30-500
A flexible sheet-like structure of g / m ² is attached. An example of the sheet-shaped structure is as follows.

1. Woven, knitted or reticulated fiber cloth. Weight per unit area is 20 to 200 g / m ² , especially 40 to 100 g / m ² . The number of threads per cm in the longitudinal and transverse directions is preferably 2 to 20. The woven or knitted fiber fabric can be made from any desired natural or synthetic yarn. But cotton thread, or relatively high E
Hydrophobic yarn with modulus (eg polyester)
Alternatively, woven or knitted fabrics made from mixed yarns consisting of both fibers and hydrophilic natural or synthetic yarns or fibers (eg cotton or polyamide) are preferably used.

2. Glass fiber woven, knitted or reticulated fiber cloth. The weight per unit area is 60 to 500 g / m ² , especially 100 to 400 g / m ² , and the E modulus is 7,000 to 9,000 (daN / mm ² ) made from glass, and the number of threads per 1 cm in the longitudinal direction is 3-10
A woven fiber cloth made of glass fibers, preferably 5 to 7 and 3 to 10, preferably 4 to 6, yarns per cm in the transverse direction is preferably used. Particularly preferred is a degree of elongation in the longitudinal direction of 10 to 40%. This fiber cloth may or may not be sized.

3. Bonded or unbonded or kneaded nonwovens based on inorganic or preferably organic fibers. A weight per unit area of 30 to 400 g / m ² , and particularly 50 to 200 g / m ² is suitable.

Nonwoven fabrics having a weight per unit area of up to 1,000 g / m ² can also be used in the form of jackets or splints for the cured coating material according to the invention. Carrier materials suitable for the present invention are described, for example, in US Pat.
4,134,397, 3,686,725, 3,882,857, German Patent Publication No. 3,211,634 and European Patent A
-61,642.

The synthetic dispersions for the layered coating materials according to the invention are generally polyurethanes and / or polyurethaneureas, which are chemically incorporated with hydrophilic groups which confers dispersibility in water.

This hydrophilic group is (a) an ionic group, and / or (b) a group which can be converted into an ionic group by a neutralization reaction, and / or (c) a poly (urethane) -introduced poly ethylene oxide units in the polyether chain (-CH ₂ -CH ₂ -O
-).

All polyurethane (urea) aqueous dispersions are known per se and, when dried, form a non-sticky film that contains alcohols or other organic solvents and are therefore less sensitive to coagulation by electrolytes. It can be used for the production of synthetic dispersions.

Several methods of producing aqueous dispersions of polyurethane (urea) are known. The review is Angewantte Macromolleclare Chemie (Angew.Makr.Chem.), 26 , 85-10.
6 (1972), Angewante Chemie, 82 , 53-63 (1
970), Journal Oil Collected Chemistry Association (J. Oil Col. Chem. Assoc.), 5
3 , 363-379 (1970), Angewante Macromolerere Hemmy, 78 , 133-158 (1981), and "Hemi und Technological Micro-Moleculare.
Stoffee (Chemie und Technologie makromolekulare
r Stoffe ”[at Aachen University of Technology 19
The 29th publication of the Department of Chemical Engineering, Aachen Institute of Technology on the 9th Colloquium held on May 8, 1981].

A preferred method of making an aqueous polyurethane (urea) dispersion to carry out is to dissolve the isocyanate prepolymer in an organic solvent and react it with a chain extender. In this case either the prepolymer or the chain extender contains ionic or ion-forming groups. The groups capable of forming ions are converted to ionic groups during or after the polyaddition reaction. Simultaneously or afterwards, water is added and the organic solvent is distilled to obtain an aqueous dispersion. As mentioned above, cationic, anionic and nonionic polyurethane dispersions can be used in the process of the invention. Preferably an aqueous polyurethane (urea) dispersion is used which yields a polyurethane film with elasticity when dried. Such a film has an elastomeric, or at least impact-resistant, ball depression hardness of 1,400 kp / cm ² (DIN 5
3,456 by 60 seconds), preferably a film of polyurethane, polyurea or polyhydrodicarboxamide having a Shore D hardness of less than 98.

Other synthetic dispersions suitable for the present invention are polyvinyl acetate based aqueous dispersions used in the civil engineering industry.
Examples are ethylene / vinyl acetate copolymers and vinyl laurate / vinyl acetate copolymers [Plastic
Plaste und Kautschuk magazine, 1
7 , 162 (1970)].

The preferred synthetic dispersions for the layered coating material of the present invention are stable to calcium and / or sulfate ions. A particularly preferred synthetic dispersion for the layered coating material of the present invention is a water-dispersible polyurethane having a substantially linear molecular structure having the following characteristics.

a) 0.5-10% by weight of ethylene based on total polyurethane
It has a terminal polyalkylene oxide-polyether containing oxide units.

b) 100 g per ^{= N + =, = S +} , -COO - or -SO ₃ ^- content of groups is 0.1 to 15 meq.

The laminated coating material of the present invention comprises at least one cast layer and one synthetic resin layer, the outer layer preferably being a cast layer.

The layered coating material of the present invention generally has 2-7, preferably 3-5, alternating plaster layers and synthetic resin layers.

In the laminated coating material of the present invention, at least the dressing layer used to make the cast layer is finished with the synthetic dispersion. However, it is also possible in the present invention to impregnate both the dressing layer forming the cast layer and the bandage layer forming the plastics layer with the aqueous synthetic dispersion.

The degree of solids impregnation of the dispersion is generally 1 for a particular layer.
-10, preferably 2-5% by weight.

The invention also provides a process for the production of the laminated coating material according to the invention, wherein separate layers of cast and synthetic resin are each attached to a carrier material. This method is characterized in that at least the cast layer used and optionally the synthetic resin layer are treated with an aqueous dispersion of plastic, and then the cast layer and the synthetic resin layer are alternately stacked.

The laminated coating material of the present invention can be produced, for example, as follows.

A cast layer (cast bandage) mounted on a carrier material is dipped in an aqueous dispersion of synthetic resin and immediately wrapped without further pressing on the body to be supported in a moist state, optionally together with a substrate material, Is first coated. After coating one cast layer, a synthetic resin layer (resin bandage) is coated on the wet cast. However, the resin bandage may be first dipped in water and optionally impregnated with the aqueous synthetic dispersion.

In this way other cast layers and synthetic resin layers can be wound alternately.

In the method for producing a laminated coating material of the present invention, the synthetic resin layer and the cast layer have a concentration of 1 to 50, preferably 2 to 20% by weight.
Immerse in the aqueous synthetic dispersion of.

The aqueous synthetic dispersion may contain other water-soluble organic solvents such as alcohols (eg methanol or ethanol) or acetone in an amount of 1 to 20, preferably 2 to 10% by weight.

The plaster cast and, optionally, the synthetic resin bandage are saturated with the synthetic dispersion. Immersion for 2-10 seconds generally provides adequate saturation.

In the present invention, it is important that the cast dressing contains an aqueous synthetic dispersion when cured.

In accordance with the invention, a laminated coating material is made using 2-7 layers of cast and synthetic resin, each attached to a carrier material, at least the cast layer being finished with an aqueous synthetic dispersion. You can

Especially surprisingly, unlike the cast coating material impregnated with an aqueous polyurethane (urea) dispersion as described in EP 128,399, the laminated coating material of the present invention cures rapidly. , Easily release excess water.

Although the laminated coating material of the present invention has excellent resistance to water, it is characterized by unimpeded water transport, high elasticity, and high stability against breakage. Notably, the laminated coating material of the present invention does not break or shatter edges. The adhesion between the individual layers of the laminate is very high as compared to the laminated coating material without the finish.

The laminated coating material of the present invention is particularly suitable as a supporting coating material for immobilizing parts of the human and animal body.

Examples The following ingredients were used in the following examples.

1. Gypsum bandage Commercial plaster bandage [Bipratrix] Biplatri
x) , West Germany, made by Baiersdorf],
500-600 / cm for cotton knit carrier²Covered with a cast
use.

2. Synthetic resin bandage Weight per unit area is 60 ± 10g / cm²150 ± 20 for cotton knitting
A commercially available synthetic resin bandage coated with wt% polyurethane
use. The polyurethane contains aromatic isocyanate groups.
The NCO content is 18 ± 2% by weight and the viscosity (25 ° C) is 10,
It was 000 to 25,000 mPa. [Deltacast (Deltacas
t) , West Germany, Johnson & Johnson
on & Johnson) company].

3. Synthetic dispersion a) Polyurethane (PU) dispersion The PU dispersion used below can be prepared as follows. 1,632 parts of a polyester diol consisting of hexane-1,6-diol, 2,2-dimethylpropane-1,3-diol and adipic acid and having an OH number of 63 at 14 mmHg at 1000 ° C.
After dehydration under vacuum, and adding 85 parts of polyether monoalcohol consisting of n-butanol, ethylene oxide and propylene oxide (molar ratio 83:17) and having an OH value of 30, 24
A mixture of 4.2 parts of 3-isocyanatomethyl-3,5,5-trimethylhexylisocyanate and 185 parts of hexane-1,6-diisocyanate is added. NCO this mixture
Stir at 100 ° C. until the content is 4.6% by weight. 50
After cooling to ~ 60 ° C, 3,200 parts of anhydrous acetone was added. A mixture of 107 parts of sodium (2-aminoethyl) -2-aminoethanesulfonate and 10 parts of hydrazine monohydrate is dissolved in 260 parts of water and slowly added to this acetone solution. After stirring the mixture for a further 10 minutes, 2,
Add 280 parts of water slowly with vigorous stirring. A pale white dispersion is obtained containing the solids in water and acetone.
After removing the acetone by distillation, an aqueous dispersion with a solids concentration of 50% results. The diameter of the particles was measured by the light scattering method, and a value of 200 ± 20 nm was obtained.

The solids content of the dispersion contained 3.1% polyethylene oxide moieties and 3 milliequivalents of sulfonic acid groups (-
SO ₃ ^-) it contained.

b) Polyvinyl (EVA) dispersion A commercially available aqueous dispersion of a copolymer of vinyl acetate and ethylene.
Stuff. pH = 4, particle size 0.5-1 μm, 53%, viscosity 8000 millipa
Skull / sec [Vinnapas] Dispersion, LT 4
41, West Germany, Wacker-Chemie
Manufactured by the company), see the company publication No. 3710,283].

Example 1 (Manufacture of Finishing Cast Bandages) 14 casts of 8 × 400 cm size (dry weight about 1 each)
70 g) are each dipped 4 to 5 times in 1900 g of a PU dispersion with a concentration of 5% by weight, until no air bubbles are formed. The bandage is lightly squeezed, removed and processed into test pieces corresponding to the examples below. The amount of the remaining dispersion is as follows. Amount 780g,
Solid content 5.65% by weight.

This means that after treatment with the PU dispersion, 14 cast plasters incorporated up to 51 g of solids in the synthetic dispersion, which corresponds to a degree of impregnation of 2.3%.

Example 2 A test piece was wound as follows.

Inner diameter 87 mm Width 90 mm Specimen A 1st layer: A plaster bandage having a size of 10 × 300 cm is immersed in water for 5 seconds, squeezed and wound three times around the corresponding spool (diameter 87 mm).

Second layer: A synthetic resin bandage of size 10 × 300 cm is dipped in water for 5 seconds, squeezed and then wound twice on the existing cast layer.

Third layer: Another cast plaster of size 10 × 300 cm is dipped in water for 5 seconds and wrapped 3 times over the existing synthetic resin bandage. After curing and removing the spool, the breaking strength in the radial direction is 1
A molded product of 5.5 N / cm was obtained.

[Measured according to Zwick No. 1484, the test piece was sandwiched between plates, and the maximum forward speed was 25 mm / min].

Specimen B First layer: Same as A, but with a concentration of 10% by weight instead of water
Immerse in EVA dispersion.

Second layer: same as A.

Third layer: same as A, but with a concentration of 10% by weight instead of water
Immerse in EVA dispersion.

Breaking strength: 19.1 N / cm (determined as in A).

Specimen C First layer: Same as A, but with a concentration of 10% by weight instead of water
Immerse in PU dispersion.

Second layer: same as A.

Third layer: same as A, but with a concentration of 10% by weight instead of water
Immerse in PU dispersion.

Breaking strength: 19.1 N / cm (determined as in A).

Example 3 A test piece was wound as follows.

Inner diameter 100 mm, width 90 mm Specimen A 1st layer: A plaster bandage having a size of 8 × 400 cm is immersed in water for 5 seconds, squeezed and wound three times around the corresponding spool (diameter 10 cm).

Second layer: A synthetic resin bandage of size 7.5 × 300 cm is immersed in water for 5 seconds, squeezed and then wound twice on the existing cast layer.

Third layer: Another cast plaster of size 8 × 400 cm is dipped in water for 5 seconds and wrapped 3 times over the existing synthetic resin bandage. After curing and removing the spool, the breaking strength in the radial direction is 1
A molded product of 2.2 N / cm was obtained.

[Measured by Zwick No. 1484, the test piece was sandwiched between plates, and the maximum forward speed was set to 25 mm / min].

Specimen B First layer: Same as A, but with a concentration of 5% by weight instead of water
Immerse in PU dispersion.

Second layer: same as A.

Third layer: same as A, but with a concentration of 5% by weight instead of water
Immerse in PU dispersion.

Breaking strength: 13.6 N / cm (determined as in A).

Specimen C First layer: B Same.

Second layer: same as A, but with a concentration of 5% by weight instead of water
Immerse in PU dispersion.

Third layer: same as B.

Breaking strength: 14.6 N / cm (determined as in A).

Example 4 A test piece was wound as follows.

Inner diameter 100 mm Width 200 mm Specimen A: Same as Specimen A of Example 3, but size 10
Uses a 300 cm plaster bandage.

Specimen B: Same as Specimen B of Example 3, but size 10
Uses a 300 cm plaster bandage.

Maximum load in the longitudinal direction (crushing or delamination) (= static)
Was measured on the test piece.

Test piece A: 12 kp Test piece B: 100 kp Example 5 A test piece was wound as follows.

Inner diameter 87 mm, width 100 mm Test piece A First layer: A synthetic resin bandage having a size of 10 × 400 cm is immersed in water for 5 seconds, squeezed, and then wound three times around the corresponding spool (diameter 87 cm).

Second layer: A 10 × 200 cm size synthetic resin bandage (degree of plaster coating 510 ± 20 g / m ³ ) is dipped in water for 5 seconds, squeezed and then wrapped 4 times over the existing synthetic resin layer.

Specimen B First layer: Same as A, but with a concentration of 5% by weight instead of water
Immerse in PU dispersion.

Second layer: same as A, but with a concentration of 5% by weight instead of water
Immerse in PU dispersion.

After curing and removing the spool, a molded product with a radial breaking strength of 11.4 N / cm for A and 12.4 N / cm for B was obtained.
[Measured by Zwick No. 1484, the test piece was sandwiched between plates, and the maximum forward speed was set to 25 mm / min].

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Datemar Schiepel Germany Day 5000 Cologne 80, Johannitasyutrase 15 (72) Inventor Datemar Schyutratzhe Federal Republic of Germany Day 3220 Alfert Ambalde 11

Claims (8)

[Claims] 1. A method comprising: a cast layer attached to a carrier material and a separate layer of water-curable synthetic resin, at least the cast layer being a synthetic dispersion of polyurethane.
Laminated coating material, characterized in that it is finished with a synthetic dispersion of polyurethaneurea or a synthetic dispersion based on polyvinyl acetate. 2. The laminated coating material according to claim 1, wherein water-curable polyurethane or water-curable polyvinyl alcohol is used as the synthetic resin. 3. Laminated coating material according to claim 1 or 2 which uses a synthetic dispersion stable to calcium ions. 4. The laminated coating material according to claim 1, wherein a woven or knitted fabric of cotton and / or synthetic fibers and / or glass is used as a carrier material. 5. The laminated coating material according to any one of claims 1 to 4, wherein at least one cast layer and at least one synthetic resin layer are used. 6. Laminated coating material according to any of claims 1 to 5, wherein a cast layer is used as the outer layer. 7. A laminated coating material according to claim 1, wherein 2 to 7 cast layers and synthetic resin layers are alternately used. 8. The degree of impregnation is 1-10% by weight with respect to the particular layer.
The laminated coating material according to any one of claims 1 to 7.